CN104163756A - Synthetic method of 2-hydroxy-4-methoxybenzophenone - Google Patents
Synthetic method of 2-hydroxy-4-methoxybenzophenone Download PDFInfo
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- CN104163756A CN104163756A CN201410215535.0A CN201410215535A CN104163756A CN 104163756 A CN104163756 A CN 104163756A CN 201410215535 A CN201410215535 A CN 201410215535A CN 104163756 A CN104163756 A CN 104163756A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/64—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of functional groups containing oxygen only in singly bound form
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/008—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with tri- or tetrahalomethyl compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
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- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a synthetic method of 2-hydroxy-4-methoxybenzophenone. The method comprises the following steps: condensing main raw materials comprising benzenyltrichloride and resorcinol, methylating, and purifying to obtain a final product. Compared with traditional synthetic methods, the synthetic method of 2-hydroxy-4-methoxybenzophenone has the advantages of reduction of Friedel-Crafts and hydrolysis reaction steps through primarily carrying out condensation, simple reaction technology and easy operation; the set of a feed ratio makes the reaction full and complete, so a largest yield is guaranteed; and the final product is obtained through filtering, re-crystallizing and purifying, the purity of the product can reach 95-98%, and the yield of the product can reach above 90%.
Description
Technical field
The synthetic method that the present invention relates to a kind of ESCALOL 567, belongs to the field of chemical synthesis.
Background technology
ESCALOL 567 is for plastics, chemical fibre, paint and petroleum product, be specially adapted to light-coloured transparent goods, can be used for paint and various plastics, effective especially to polyvinyl chloride, polyester, vinylformic acid, resin, polystyrene and light-coloured transparent furniture etc., good cosmetics additive especially.Benzophenone UV light absorber, is the good stable agent of the synthetic plasticss such as polyethylene, and consumption is 0.5～1.5%, also can be used in the cured and daily cosmetics of paint, pigment, coatings industry, pure white.It is a kind of wide spectrum UV light absorber, have specific absorption high, nontoxic, without teratogenesis, to the advantage such as light, Heat stability is good, it can absorb UV-A and UV-B simultaneously, it is the I class sun-screening agent of U.S. FDA approval, higher in US and European frequency of utilization, be widely used in suntan lotion, frost, honey, emulsion, wet goods sun care preparations, also can be used as the resistance toner of the product of the variable color by photosensitivity.
At present, the traditional technology of ESCALOL 567 is taking Resorcinol, Benzoyl chloride, chlorobenzene etc. as raw material, through traditional methylating, the reaction such as Friedel-Crafts, hydrolysis is synthetic, complex manufacturing, product purity is low, product yield is low is only 50～55%, adopt 2 at present now, 4-dihydroxy benzophenone and methyl-sulfate are directly synthetic ESCALOL 567 of raw material, but prior art complex manufacturing, product purity is low, and the phenomenon that product yield is low still exists.
Therefore be badly in need of a kind of synthetic method of safe, simple, yield is high, product purity is high ESCALOL 567, meet the need of production of ESCALOL 567.
Summary of the invention
The object of this invention is to provide a kind of synthetic method of ESCALOL 567, with trichlorotoluene zotrichloride, the improved condensation of Resorcinol main raw material, the step that methylates, again by the refining the finished product that obtain, reaction is simple, easy to operate.
The technical solution used in the present invention is: a kind of synthetic method of ESCALOL 567, comprise condensation step and the step that methylates, its innovative point is: first described condensation step for preparing raw material and reagent, the molar ratio of raw material and reagent is: Resorcinol: trichlorotoluene zotrichloride: catalyzer: solvent=1:1～1.2:0.1～0.3:5～10, first add solvent and Resorcinol to mix by proportioning, be warming up to completely and dissolve, add again catalyzer, then drip trichlorotoluene zotrichloride, in dropping process, control temperature and keep 45～55 DEG C, dropping is reacted after finishing, controlling temperature of reaction is 55～70 DEG C, reaction times is 5.5～6.5h, after finishing, reaction is warming up to 70～75 DEG C, insulation 1～1.5h obtains 2, 4-dihydroxy benzophenone, by 2, 4-dihydroxy benzophenone solution is cooled to 20 DEG C and filters after following, finally with 50～60 DEG C of hot water, filtrate is washed till to neutrality, 80～85 DEG C of oven dry, drying time is 6～6.5h.
The reaction formula of condensation step:
Further, first the described step that methylates for preparing material and reagent, the molar ratio of material and reagent is 2, 4-dihydroxy benzophenone: methide: sodium hydroxide: water=1:1.2～1.5:1～1.3:25～30, first by sodium hydroxide water dissolution, after being cooled to 5～8 DEG C, add again 2, 4-dihydroxy benzophenone, be cooled to below 0 DEG C, dripping methide reacts, controlling temperature of reaction is 0～2 DEG C, reaction times is 6～6.5h, reaction finishes final vacuum and pumps solvent, the cut of 160 DEG C/5mmHg is collected in underpressure distillation again, finally filter or recrystallization obtains product.
The reaction formula of the step that methylates:
Further, described catalyzer is zinc chloride or aluminum chloride.
Further, described solvent is ether, methyl tertbutyl ether, methyl alcohol or ethanol.
Further, described methide is methyl-sulfate or methylcarbonate.
Further, the control of the time of described dropping trichlorotoluene zotrichloride is 1～2h.
Further, the control of the time of described dropping methide is 1～2h.
Beneficial effect: the synthetic method of this ESCALOL 567 of the present invention, than traditional synthetic method, first carry out having lacked the reactions steps such as Friedel-Crafts, hydrolysis after condensation, reaction process is simple, easy to operate; The setting of method feed ratio of the present invention, makes sufficient reacting complete, provides guarantee for obtaining maximum yield ratio; Method of the present invention obtains the finished product by filtration, recrystallizing and refining, and product purity can reach 97～99%, and product yield can reach more than 90%.
Embodiment
Implementation column below can make those skilled in the art more fully understand the present invention, but does not therefore limit the present invention among described scope of embodiments.
embodiment 1
Condensation reaction: add solvent methanol 180ml in 500ml there-necked flask, Resorcinol 66g, after rising temperature for dissolving, then adds catalyzer zinc chloride 6g, then be warming up to 45 DEG C, starts to drip trichlorotoluene zotrichloride 135g, controls temperature and is no more than 55 DEG C, and 1h drips off.After temperature control 55-60 DEG C of reaction 6h, be warming up to 70 DEG C of insulation 1h again, be cooled to below 20 DEG C, filter.50-60 DEG C of hot water is washed to neutrality.80 DEG C of 6h are dried, and the product of gained is 124g.
Methylation reaction: in the there-necked flask of 250ml, add sodium hydroxide 8.2g, after 100ml water dissolution, be cooled to 5 DEG C.Add 2,4-dihydroxy benzophenone 42.8g, then be cooled to below 0 DEG C, start to drip methyl-sulfate 30.6g, control time for adding 1h.Dropwise, control temperature more than 0-2 DEG C of stirring reaction 6h, vacuum pumps solvent, then the cut of 160 DEG C/5mmHg of underpressure distillation collection, obtains product 43.3g.
In the present embodiment, the synthetic product purity of method of the present invention is 98.5%, total yield of products 91.7%.
embodiment 2
Condensation reaction: add etoh solvent 170ml in 500ml there-necked flask, Resorcinol 55g, after rising temperature for dissolving, then adds catalyzer zinc chloride 2.7g, then be warming up to 50 DEG C, starts to drip trichlorotoluene zotrichloride 102.6g, controls temperature and is no more than 55 DEG C, and 1h drips off.After temperature control 55-70 DEG C of reaction 6h, be warming up to 75 DEG C of insulation 1h again, be cooled to below 20 DEG C, filter.50-60 DEG C of hot water is washed to neutrality.80 DEG C of 6h are dried, and the product of gained is 125g.
Methylation reaction: in the there-necked flask of 250ml, add sodium hydroxide 4.1g, after 54ml water dissolution, be cooled to 5 DEG C.Add 2,4-dihydroxy benzophenone 21.4g, then be cooled to below 0 DEG C, start to drip methylcarbonate 10.8g, control time for adding 1h.Dropwise, control temperature more than 0-2 DEG C of stirring reaction 6h, vacuum pumps solvent, then the cut of 160 DEG C/5mmHg of underpressure distillation collection, obtains product 21.7g.
In the present embodiment, the synthetic product purity of method of the present invention is 98%, total yield of products 92.5%.
Claims (7)
1. the synthetic method of an ESCALOL 567, comprise condensation step and the step that methylates, it is characterized in that: first described condensation step for preparing raw material and reagent, the molar ratio of raw material and reagent is: Resorcinol: trichlorotoluene zotrichloride: catalyzer: solvent=1:1～1.2:0.1～0.3:5～10, first add solvent and Resorcinol to mix, be warming up to completely and dissolve, add again catalyzer, then drip trichlorotoluene zotrichloride, in dropping process, control temperature and keep 45～55 DEG C, dropping is reacted after finishing, controlling temperature of reaction is 55～70 DEG C, reaction times is 5.5～6.5h, after finishing, reaction is warming up to 70～75 DEG C, insulation 1～1.5h obtains 2, 4-dihydroxy benzophenone, by 2, 4-dihydroxy benzophenone solution is cooled to 20 DEG C and filters after following, finally with 50～60 DEG C of hot water, filtrate is washed till to neutrality, 80～85 DEG C of oven dry, drying time is 6～6.5h.
2. the synthetic method of ESCALOL 567 according to claim 1, it is characterized in that: described in methylate step for first preparing material and reagent, the molar ratio of material and reagent is 2, 4-dihydroxy benzophenone: methide: sodium hydroxide: water=1:1.2～1.5:1～1.3:25～30, first by sodium hydroxide water dissolution, after being cooled to 5～8 DEG C, add again 2, 4-dihydroxy benzophenone, be cooled to below 0 DEG C, dripping methide reacts, controlling temperature of reaction is 0～2 DEG C, reaction times is 6～6.5h, reaction finishes final vacuum and pumps solvent, the cut of 160 DEG C/5mmHg is collected in underpressure distillation again, finally filter or recrystallization obtains product.
3. the synthetic method of ESCALOL 567 according to claim 1, is characterized in that: described catalyzer is zinc chloride or aluminum chloride.
4. the synthetic method of ESCALOL 567 according to claim 1, is characterized in that: described solvent is ether, methyl tertbutyl ether, methyl alcohol or ethanol.
5. the synthetic method of ESCALOL 567 claimed in claim 2, is characterized in that: described methide is methyl-sulfate or methylcarbonate.
6. the synthetic method of ESCALOL 567 according to claim 1, is characterized in that: it is 1～2h that the time of described dropping trichlorotoluene zotrichloride is controlled.
7. the synthetic method of ESCALOL 567 according to claim 2, is characterized in that: it is 1～2h that the time of described dropping methide is controlled.
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| CN201410215535.0A CN104163756A (en) | 2014-05-21 | 2014-05-21 | Synthetic method of 2-hydroxy-4-methoxybenzophenone |
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| CN201410215535.0A CN104163756A (en) | 2014-05-21 | 2014-05-21 | Synthetic method of 2-hydroxy-4-methoxybenzophenone |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104610036A (en) * | 2015-01-30 | 2015-05-13 | 江苏省海洋资源开发研究院(连云港) | Method for preparing p-chlorodiphenyl ketone |
| CN106083543A (en) * | 2016-06-07 | 2016-11-09 | 安徽圣诺贝化学科技有限公司 | One prepares the method for sun-screening agent intermediate 2,4 dihydroxy benaophenonel |
| CN107879910A (en) * | 2017-11-02 | 2018-04-06 | 武汉科技大学 | A kind of green synthesis process of 2,4 dihydroxy benaophenonel |
| CN109336754A (en) * | 2018-10-23 | 2019-02-15 | 襄阳金达成精细化工有限公司 | A kind of preparation method of ultraviolet absorbing agent UV-9 |
| CN109456233A (en) * | 2018-10-23 | 2019-03-12 | 襄阳金达成精细化工有限公司 | A kind of preparation method of ultraviolet absorbing agent UV-284 |
| CN110128253A (en) * | 2019-05-05 | 2019-08-16 | 宜都市华阳化工有限责任公司 | ESCALOL 567 cleans preparation method |
| CN111302920A (en) * | 2020-01-15 | 2020-06-19 | 湖北美凯化工有限公司 | Production method of ultraviolet absorbent BP-3 |
| CN112142579A (en) * | 2019-06-27 | 2020-12-29 | 江苏紫奇化工科技有限公司 | Preparation process of 2-hydroxy-4-methoxybenzophenone |
| CN113087588A (en) * | 2021-04-07 | 2021-07-09 | 常州新东化工发展有限公司 | Continuous rectification production process of benzyl aromatic oil |
Citations (1)
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| US20020193641A1 (en) * | 2001-02-23 | 2002-12-19 | Elisabeth Borredon | Process for the synthesis of aryl alkyl monoethers |
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2014
- 2014-05-21 CN CN201410215535.0A patent/CN104163756A/en active Pending
Patent Citations (1)
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| US20020193641A1 (en) * | 2001-02-23 | 2002-12-19 | Elisabeth Borredon | Process for the synthesis of aryl alkyl monoethers |
Non-Patent Citations (3)
| Title |
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| N.R.AYYANGAR ET AL.: "(Trichloromethyl)benzene:A Versatile Reagent for the preparation of Substituted Benzophenones", 《SYNTHESIS》 * |
| 钱君律等: "紫外线吸收剂UV一9 生产新工艺", 《上海化工》 * |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104610036A (en) * | 2015-01-30 | 2015-05-13 | 江苏省海洋资源开发研究院(连云港) | Method for preparing p-chlorodiphenyl ketone |
| CN106083543A (en) * | 2016-06-07 | 2016-11-09 | 安徽圣诺贝化学科技有限公司 | One prepares the method for sun-screening agent intermediate 2,4 dihydroxy benaophenonel |
| CN107879910A (en) * | 2017-11-02 | 2018-04-06 | 武汉科技大学 | A kind of green synthesis process of 2,4 dihydroxy benaophenonel |
| CN107879910B (en) * | 2017-11-02 | 2021-06-11 | 武汉科技大学 | Green synthesis process of 2, 4-dihydroxy benzophenone |
| CN109336754A (en) * | 2018-10-23 | 2019-02-15 | 襄阳金达成精细化工有限公司 | A kind of preparation method of ultraviolet absorbing agent UV-9 |
| CN109456233A (en) * | 2018-10-23 | 2019-03-12 | 襄阳金达成精细化工有限公司 | A kind of preparation method of ultraviolet absorbing agent UV-284 |
| CN110128253A (en) * | 2019-05-05 | 2019-08-16 | 宜都市华阳化工有限责任公司 | ESCALOL 567 cleans preparation method |
| CN112142579A (en) * | 2019-06-27 | 2020-12-29 | 江苏紫奇化工科技有限公司 | Preparation process of 2-hydroxy-4-methoxybenzophenone |
| CN111302920A (en) * | 2020-01-15 | 2020-06-19 | 湖北美凯化工有限公司 | Production method of ultraviolet absorbent BP-3 |
| CN113087588A (en) * | 2021-04-07 | 2021-07-09 | 常州新东化工发展有限公司 | Continuous rectification production process of benzyl aromatic oil |
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Application publication date: 20141126 |